CN103348476A - White-light light-emitting diode lamp with remote reflective photoluminescent converter - Google Patents
White-light light-emitting diode lamp with remote reflective photoluminescent converter Download PDFInfo
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- CN103348476A CN103348476A CN201180064616XA CN201180064616A CN103348476A CN 103348476 A CN103348476 A CN 103348476A CN 201180064616X A CN201180064616X A CN 201180064616XA CN 201180064616 A CN201180064616 A CN 201180064616A CN 103348476 A CN103348476 A CN 103348476A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/60—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction
- F21K9/64—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction using wavelength conversion means distinct or spaced from the light-generating element, e.g. a remote phosphor layer
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/0008—Reflectors for light sources providing for indirect lighting
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/005—Reflectors for light sources with an elongated shape to cooperate with linear light sources
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/04—Optical design
- F21V7/043—Optical design with cylindrical surface
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
- F21V7/24—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by the material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
- F21V7/28—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by coatings
- F21V7/30—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by coatings the coatings comprising photoluminescent substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components with at least one potential-jump barrier or surface barrier specially adapted for light emission
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/20—Light sources comprising attachment means
- F21K9/23—Retrofit light sources for lighting devices with a single fitting for each light source, e.g. for substitution of incandescent lamps with bayonet or threaded fittings
- F21K9/233—Retrofit light sources for lighting devices with a single fitting for each light source, e.g. for substitution of incandescent lamps with bayonet or threaded fittings specially adapted for generating a spot light distribution, e.g. for substitution of reflector lamps
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V29/00—Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
- F21V29/50—Cooling arrangements
- F21V29/502—Cooling arrangements characterised by the adaptation for cooling of specific components
- F21V29/505—Cooling arrangements characterised by the adaptation for cooling of specific components of reflectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/484—Connecting portions
- H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
- H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention relates to white-light lamps based on semiconductor light-emitting diodes with remote photoluminescent converters. The essence of the invention is that the lamp comprises a heat-dissipating base with a radiation exit opening, and light-emitting diodes secured about the periphery of the opening, with, arranged in series at a distance from said light-emitting diodes, a radiation converter in the form of a concave layer of photoluminescent material, and a light reflector with a concave light-reflecting surface, wherein the concavities of the radiation converter and the light reflector are oriented towards the light-emitting diodes and the exit opening. When primary radiation from the light-emitting diodes falls on the surface of the converter, white light generated as a result of the mixing of the reflected primary radiation with secondary radiation from the photoluminescent material exits via the opening in the heat-dissipating base. The surfaces of the converter and the reflector may be in the form of a truncated ellipsoid of revolution, in particular a sphere, or a paraboloid, with a main axis perpendicular to the plane of the opening in the heat-dissipating base, or a cylinder which is truncated by the plane of the exit opening. In order to improve the dissipation of heat, thermal contact is provided between the convex surface of the converter and the concave inside surface of the reflector, the outside surface of which can be in the form of a ribbed heat radiator associated with the heat-dissipating base.
Description
The present invention relates to electrotechnics and electronics, particularly, the present invention relates to the light source based on semiconductor light-emitting-diode, more specifically, the present invention relates to the white light source that has fluorescent material-transducer based on semiconductor light-emitting-diode.
Have benefited from relevant high efficient LED, particularly about the newest research results of indium nitride InGaN heterojunction, the solid-state illumination technology begins to occupy white light market, and its efficient also is the highest in all known white light sources.LED is widely used in linear lighting equipment and the street lamp, and light fixture is bigger comparatively speaking in these linear lighting equipment and street lamp, and use can produce the LED of thermal effect fast, and the position of these LED of layout, effectively quantity of heat given up well.Owing to advocate energy-conservation now energetically, but the small and exquisite LED lamp with high light flux of development profile substitutes traditional incandescent lamp and Halogen lamp LED, it is the most urgent present scientific and technological problem, but because the volume of LED lamp is limited, can limit the placement of electronic-controlled installation (driver), and its thermal output surface is less relatively, and these all are that the small and exquisite LED lamp of development profile has increased difficulty.White light LEDs generally includes the blue-ray LED that covers YAG:Ce fluorescent material.When having the 550-700 milliwatt to be assigned to heater in every watt, the efficient of high-power (1 watt or more than) blue-ray LED is 30-45%.In addition, when fluorescent material is converted to gold-tinted to blue light in the white light LEDs light energy near 20% all be used to heat fluorescent material.These technical characterictics show that when temperature was 25-125 ° of C, the radiance of blue-ray LED can descend near 7%, and under same temperature, white light LEDs power can descend near 20% simultaneously.This shows that large power white light LED is having great limitation aspect heat radiation and the luminous flux.
The objective of the invention is to, develop the small and exquisite white LED lamp of a kind of profile, with technological deficiency and the alternative existing standard light fixture that solves above-mentioned existing standard light fixture.
The basis of white LED lamp of the present invention is led chip.The white light that obtains partly is that the light (for example blue light, green glow and ruddiness or blue light and orange-colored light) of the different colours that sent by the led chip of combining mixes gained.
But recent years, people are inclined to use this class white LED light source gradually, and it has fluorescent material-transducer, and when absorbing blue light that led chip gives off or ultraviolet light, it can give off gold-tinted or orange-colored light (ruddiness).Please refer to Fig. 1, Fig. 1 is this type white light source schematic diagram.
This white light source comprises led chip and a radiation conversion environment, and chip can send shortwave radiation, and this shortwave radiation is radiated on the radiation converter, and radiation converter is excited by shortwave radiation and sends the long long-wave radiation of wavelength.In concrete light compositing process, be wrapped in ultra-blue-light or the ultraviolet light that the chip in the organic or inorganic fluorescent material gives off and change into white light.
Fig. 2 be the light-emitting diode that has fluorescent material-transducer be the famous white light source equipment on basis, this white light source had description in US Patent No. 6351069.
White light source 110 comprises LED nitride chip 112, can launch initial blue light when this chip is excited.Chip 112 is placed in the interior lead frame of reflector 114 nests, couples together with electric wire and conductor 116,118.Conductor 116 and 118 transmits electric power to chip 112.Chip 112 is covered by transparent resin layer 120, and the transition material 122 that comprises to change radiation wavelength in the resin is used to form 120 transition material, can be according to the random selection of reradiative spectral distribution.Chip 112 and transparent resin layer 120 are covered by lens 124.Lens 124 are made by transparent epoxy resin or silicones usually.Apply voltage in the present invention on chip 112, chip upper surface can be launched prompt radiation.The part prompt radiation is absorbed by the transition material 122 in 120.Transition material 122 can send radiation again on the prompt radiation basis then, that is to say radiation is changed, and makes it become the light with longer peak wavelength.Another part does not have absorbed radiation by conversion layer and radiation mixing again in the prompt radiation.Lens 124 do not have absorbed prompt radiation and again radiation export together, as shown in the figure, the light that arrow 126 expressions are exported.Therefore, only the mixing of output, it comprises the radiation again that the prompt radiation that given off by chip 112 and conversion layer 120 give off.Can select to do transition material with the material that only allows the fraction prompt radiation or do not allow prompt radiation overflow, when the chip that sends the ultraviolet light prompt radiation and one or more send visible reradiative transition material and put together.
In the above-mentioned famous light source of mentioning, phosphor powder layer is formed at the surface of light-emitting diode, it has following defective: because the influence of light propagation angle when being subjected to passing phosphor powder layer, light wavelength can change a lot, therefore when the surface of fluorescent material and light-emitting diode direct photo-thermal takes place contacts, be difficult to reach the uniformity of light color; In addition, when the light-emitting diode adstante febre, very high temperature can make the chromaticity coordinates of fluorescent material change or allow its look decline.
In order to overcome above-mentioned defective, we propose that in such class white light source, in such white light source, wavelength shifter is away from light-emitting diode, and its principle as shown in Figure 3.
According to the made luminaire of this principle, once the someone did description, for example US Patent No. 6600175(B1), as shown in Figure 4.
This class white light source comprises shell 207, and internal capacity is arranged, and shell is made by transparent medium 211.Medium 211 can be made by any suitable light transmissive material, for example transparent polymer or glass.Be provided with chip 213 in the internal capacity that is coated by medium 211, chip is positioned on the base 214.First electric contact 216, second electric contact 217 respectively with chip 213 on radiant section 218 link to each other with bottom 219, wherein 218 link to each other with first electric contact 216 by conductor 212.The material of making light transmission medium 211 is fluorescence or phosphorescence component, or their mixture, in other words, is the fluorescent media that can convert radiant section 218 radiation of sending out in the light-emitting diode 213 to white light.Fluorescent material is distributed in the medium 211 of making shell 207 or overlays on the inwall of shell 207 with the form of film 209.Perhaps fluorescent material can be coated on the outer wall of shell, if shell is using (for example, under the state that extexine can not be worn and destroy) extexine also can be in good operating state under the state of nature.Fluorescent material can be distributed in polymer or the glass melt, forms shell then thus, exports from its surface with the uniformity and the light that ensure outer shell component.
The white light LEDs light fixture of famous band tubular transducer has been described in US Patent No. 7618157B1.Its device schematic diagram as shown in Figure 5.Light fixture 310 comprises the heat sink 312 of a strip, many light-emitting diodes 314, these light-emitting diodes are installed on the heat sink along the long one side of heat sink successively, light fixture also comprises hemisphere lampshade 316, it is positioned on 312 314 top, at the position of hemisphere lampshade 316 section arcs, the direction opposite with light-emitting diode 314 contain the light activated fluorescent material that can be sent by light-emitting diode.Heat sink 312 is made by Heat Conduction Material, for example aluminium.Hemispheric lampshade 316 is made by the transparent material of types such as glass or plastics.Fluorescent material 320 can be used as on the inwall that cover layer is attached to the hemisphere lampshade or with fluorescent material and put into as tectal material.The level and smooth part 326 that does not contain fluorescent material on the lampshade is positioned at the both sides of LED on the heat sink 312, it has internal reflection surface 328, aluminium cover layer for example, it can reflect light-emitting diode 314 and project light on it, reflects it on the part position 318 on the hemisphere lampshade.
Conversion layer can be fluorescent material, the mixing of quanta point material or these materials, even can also be transparent host material, in this material, contain phosphorus or quanta point material.
As everyone knows, the conversion layer that comprises phosphor powder can permeate, absorption, reflection and scattering throw light thereon.In the time of the conversion layer scattered light, it also simultaneously can permeate, absorption and reflecting part be by the light of its scattering.
The defective of foregoing invention is, by the radiation of led radiation institute excited fluorescent powder particles and the reflection of light-emitting diode, all absorbed by the componentry of phosphor powder layer and lamp interior inevitably, thereby causes the reduction of white light source efficient.
Yamada[1] and Narendran[2] determined the radiation ratio that YAG:Ce fluorescent material conversion layer is propagated back and forth, this fluorescent material can be blue-light excited about 470nm by wavelength, converts the gold-tinted radiation of long wave band then to.Narendran confirms, having 60% the light that is converted layer emission and reflection all can project excitation source and major part all can be in inner disappear [2] of light-emitting diode.Confirming in the process of the test [3], is 1.8 even work as refraction coefficient, and density is 8mg/cm
2YAG:Ce fluorescent material and refraction coefficient be that 1.6 epoxy resin mixing energy obtains stablizing white light, the radiation share that reflects in blue light and the gold-tinted radiation and the radiation share of launching also are respectively 53% and 47%, accordingly, single concerning the gold-tinted radiation, share is respectively 55% and 45%.
For reason given above, under the same situation of other conditions, also can obtain the white LED light source of the band radiation converter that has a clear superiority in luminous flux and efficient, directly the light delivery outlet on the led light source that has radiation converter is invested in the radiation that is given off by phosphor surface of being reflected by the LED radiation.
The similar techniques solution had description in US Patent No. 7293908B2; the system that shows up of a claimed a kind of output radiation from the side of embodiment in the patent; according to this patent, illuminator comprises the conversion layer away from light-emitting diode, and it is positioned on the reflective optical system.
The lighting apparatus that this patent is described and the present invention are immediate, thus we to select the lighting apparatus of this patent be prototype of the present invention.
According to this United States Patent (USP), the operation principle of the white light source of output radiation from the side as shown in Figure 6.Fig. 6 has showed one of its claimed embodiment with the form of profile to us; The illuminator of output radiation from the side.
The illuminator of output radiation from the side comprises light-emitting diode 402, the first reflectors 404, the second reflectors 406, light delivery outlet 412, conversion layer 602, additional transparent covering layer 408 and supporting tool, supporting tool is used for supporting first reflector 406 and second reflector 404, and with its separation.Supporting tool comprises level and smooth transparent element 502, the support 504 of side and base 506.The support 504 first-selected materials transparent or that have reflection function of side.First reflector 404 is fixed on the base 506, and second reflector 406 is fixed on the level and smooth transparent element 502.Conversion layer 602 is positioned at the surface of second reflector 406, and the part prompt radiation that light-emitting diode 402 can be sent at least converts the long-wave radiation that is different from the prompt radiation wavelength to.
We illustrate light beam 414,415,416 operation principle of the illuminator of output radiation from the side as an example.Incipient beam of light 414 penetrates from light-emitting diode 402, invests 402 light output surface.Incipient beam of light 414 is passed 402 light output surface, invests transparent covering layer 408.Incipient beam of light 414 is passed transparent covering layer 408, invests conversion layer 602, and conversion layer converts incipient beam of light 414 to second light beam 415 different with it.Second light beam can be transmitted into any direction from the wavelength transfer point.Second light beam 415 passes transparent covering layer 408 and light delivery outlet 412 is invested first reflector 404.Second light beam 416 is invested level and smooth transparent element 502 by first reflector, 404 reflection backs.Second light beam 416 passes 502 and exports from this illuminator.
The defective of this system is the light loss of light outlet aperture, the light loss at supporting tool edge and the light loss of throwing on the reflector.
The famous white light source of the another kind of searchlight type described in the US Patent No. 7810956B2 attempts to overcome these defectives.
Fig. 7 is the profile of this searchlight, and it is to make according to an embodiment among the US Patent No. 7810956B2, and profile has been showed design and the operation principle of this equipment.Light source 730 be installed in support 734 and additional radiator 736 on.Radiator 736 is can be gelled, as shown in Figure 7.The light that light source 730 is launched is reflected by the eyeglass 732 around light source 730, projects then on the tabula rasa 738.Wavelength conversion layer 742 is what to separate with light source 730, and it will be installed in the position that can absorb the light of launching from light source 730.Additional radiator 744 can make conversion layer 742 coolings.Integrated optics instrument 740 can make light become straight line.Can send short wavelength light, for example the light-emitting diode of blue light or ultraviolet light can be used as light source 730.730 can be installed in the additional support 734 and link to each other with additional radiator 736.Tabula rasa 738 will be installed in can be to the position of integrated optics instrument 740 projection lights.For example, 748 side can be tilted or be crooked, so that the luminous energy of its internal reflection projects on the integrated optics instrument 740.
There is the defective of light loss in this system, as the light loss that the aperture goes out, and the light loss at tabula rasa edge, these have all reduced the efficient of this system.In addition, the small and exquisite light fixture of traditional profile has very wide radiation rising angle, but the lamp of this system is very narrow from the light beam that collimating optical system gives off, therefore be not suitable for substituting the small and exquisite light fixture of traditional profile with similar light fixture, or even Halogen lamp LED.
The present invention has following purpose: assurance has the luminous efficiency of the white LED light source maximum of transducer; Guarantee the uniformity of light color height; Under the small and exquisite situation of light fixture profile, guarantee wide rising angle.
Proposed light fixture, comprise the prompt radiation light source, all around smooth heat dissipation base, towards the reflector that has light reflective surface of LED, can convert prompt radiation to reradiative conversion layer, wherein primary light source is made up of one or more LED, LED is fixed on the heat dissipation base, and conversion layer is between LED and reflector.Want to reach purpose of the present invention, we propose, need to leave the aperture on the heat dissipation base for radiation output, LED is installed in position near aperture edge on the base, the light radiation that LED sends is to the surface of conversion layer, the reflective optical system surface is spill, recess subtend prompt radiation light source and aperture.
Fig. 8 is profile of the present invention, has showed essence of the present invention in schematic form.
Light fixture comprises prompt radiation light source, heat dissipation base 2, reflector 5, conversion layer 7, wherein, the prompt radiation light source is made of one or more LED1, have aperture 3 and surface 4 on the heat dissipation base, LED1 is fixedly arranged on the susceptor surface, reflector has the light reflection surface 6 towards the spill of LED, conversion layer 7 can convert prompt radiation 8 to radiation again 9,7 have the concave surface 10 towards LED1, and towards second convex surface 11 of light reflection surface 6, and conversion layer 7 is between LED2 and reflector surface 6.
Operation principle of the present invention is as follows.The prompt radiation 8 of light-emitting diode 1 projects on the surface 10 of conversion layer 7, and partly by 10 reflections, the light of reflection enters on the aperture 3 of heat dissipation base 2, partly scattered on the conversion layer 7 after the reflection of fluorescent powder grain surface, the light of scattering is partly absorbed by 7 and converts radiation again 9 to, part prompt radiation 8 projects on the light reflective surface 6, and 6 reflect it on the conversion layer 7, and prompt radiation is converted layer 7 absorption again and forms radiation again 9.Prompt radiation 8 parts penetrate to be invested aperture 3 on the light fixture from conversion layer, mix the radiation of formation white light with radiation 9 again.The distribution of radiation is to be determined by the properties of materials of making conversion layer, at first is to be determined by the dispersiveness of its composition, fluorescent material and the thickness of conversion layer.
Inorganic optical material is fluorescent material normally, and it is synthetic by rare earth element (lanthanide series) or elements such as chromium, titanium, vanadium, cobalt or neodymium.Lanthanide series is: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.Inorganic optical material comprises (but being not limited to): sapphire (Al
2O
3), GaAs (GaAs), aluminizing oxide (BeAl
2O
4), magnesium fluoride (MgF
2), indium phosphide (InP), gallium phosphide (GaP), yttrium-aluminium-garnet (YAG or Y
3A1
5O
12), contain garnet terbium, yttrium-aluminium-lanthanum oxide, yttrium-aluminium-lanthanum-gallium oxide mixture, yittrium oxide (Y
2O
3), calcium halophosphate activated by antimony andmanganese or halogen strontium phosphate or halogen barium phosphate (Ca, Sr, Ba)
5(PO4)
3(Cl, F), CeMgAl
11O
19, lanthanum orthophosphate (LaPO
4), lanthanum-five boric acid (lanthanide series) (М r, ZnB
5O
10), BaMgAl
10O
17, SrGa
2S
4, compound (Sr, Mg, Ca, Ba) (Ga, Al, In)
2S
4, SRS, ZnS and silicic acid nitrogen.
Also have some more common fluorescent material, it can be that ultraviolet radiation about 250nm excites by wavelength.Common red light fluorescent powder-Y
2O
3: Eu
+ 3Common gold-tinted fluorescent material-YAG:Ce
+ 3Common green light fluorescent powder: CeMgAl
11O
19: Tb<3+ 〉, (lanthanide) PO
4: Ce
+ 3, Tb
+ 3And GdMgB
5O
10: Ce
+ 3, Tb
+ 3Common blue light fluorescent powder-BaMgAl
10O
17: Eu
+ 2(Sr, Ba, Ca)
5(PO
4)
3Cl:Eu
+ 2Concerning the LED of excitation wavelength about 400-450nm, more common inorganic optical material comprises yttrium-aluminium-garnet (YAG or Y
3Al
5O
12), contain the terbium garnet, yittrium oxide (Y
2O
3), YVO
4, SrGa
2S
4, (Sr, Mg, Ca, Ba) (Ga, Al, In)
2S
4, SrS and silicic acid nitrogen.The common LED of excitation wavelength between 400-450nm comprises YAG:Ce with fluorescent material
+ 3, YAG:Ho
+ 3, YAG:Pr
+ 3, SrGa
2S
4: Eu
+ 2, SrGa
2S
4: Ce
+ 3, SrS:Eu
+ 2With silicic acid nitrogen.
Quanta point material-inorganic semiconductor particle size is about 30nm.Quanta point material commonly used comprises (but being not limited to listed) CdS, CdSe,, ZnSe, InAs,, particulates such as GaAs and GaN.Quanta point material can absorb the light that has only single wavelength and then convert thereof into different wavelength, and this depends on the size of particulate certainly, the characteristic of microparticle surfaces and the characteristic of semiconductor inorganic materials.
Conversion layer can be single fluorescent material or quanta point material, also can be the mixture of fluorescent material and quanta point material.
Use mixture that certain effect is arranged, if want to allow the white light radiation of the high-color rendering launched that the wideest band is arranged.A kind of method that obtains having the white light of high color rendering index (CRI) is to allow the radiation of InGaN LED and gold-tinted and the ruddiness of fluorescent material conversion layer mix.Conversion layer can contain several fluorescent material that can absorb LED light and can give off the longer light of wavelength.For example, for blue-ray LED, conversion layer can only contain a kind of fluorescent material that can send gold-tinted, perhaps contains several fluorescent material that can give off the fluorescent material of blue-yellow light or can give off indigo plant, Huang and ruddiness.Also can add the fluorescent material that some can give off other light, with chromaticity coordinates and the color rendering index of the mixed light that sends of control light fixture.
Main material transparent can be inorganic polymer material.Polymeric material can be (but being not limited to): acrylics, polycarbonate, fluoroakrilaty, perfluoroakrilaty, fluorofosfinatnye polymers, fluorosilikony, fluoropoliimidy, politetrafluoretilen, fluorosilikony, sol-gels, epoxy resins, thermoplastics, shrink plastics and silicones.Be the most suitable less than the ultraviolet wave band of 400nm and wavelength greater than the infrared ray wave band fluoropolymer of 700nm at wavelength, because fluoropolymer is very low at the absorptivity of these wave bands.Common inorganic material has (but being not limited to): silicon dioxide, optical glass and chalcogenide glass.
The fluorescent material conversion layer can be with spraying plating, smear, precipitate or cover the surface of reflective optical system successively as cover layer from methods such as phosphor suspension electrophoresises.Certain problem can occur but cover reflector with fluorescent material, one of problem is how could be coated onto the fluorescent material conversion layer equably on the reflector, and especially the air spots when reflector is sliding, and for example, its surface is cylindrical shape or hemisphere.When the method for using spraying plating, smear and precipitating, use suspension, so that fluorescent powder grain can be coated on the base.The viscosity that can mulched ground evenly depends on suspension to a great extent, the concentration of fluorescent powder grain in suspension and environmental factor on every side, for example, temperature and humidity on every side.Owing to the mobile tectal destruction that causes of suspension, every day, overburden cover can change before cover layer becomes dry, and these all are the problems that can occur when covering reflective optical system with fluorescent material.
Be more prone in some cases fluorescent material put into and do tectal material, for example the acrylic filament that forms of transparent polycarbonate type transparent plastic, PET, polypropylene, polyethylene, extruding.Conversion layer can be beforehand with flakiness, and then is cast as required shape by heat treatment.Can be in the past before being shaped wherein the surface of a thin slice with the method casting last layer of airless spraying by aluminium or the silver-colored reflection layer of making.
Cast the conversion layer at the fin reflecting surface in advance, can be bonded at the surface of fin, for example use the agent of organosilicon gluing, available it is bonding more together with a plurality of conversion layers, and near conversion layer and the fin surface of the backing that will disperse is bonded together.Containing glue-line can be very thin, for example thin than conversion layer, and the heat that conversion layer is got rid of can not produce big thermal resistance like this.
In one of embodiment of light fixture, used multilayer luminescence generated by light thin slice to do transducer, thin slice is bonded on the reflector of cylindricality copper or brass, the thin aluminium of one deck (0.5 micron) is arranged on the reflector, and this is to use the method for vacuum thermal spraying that aluminium lamination is cast onto on the reflector.
The suspension that contains fluorescent material, surface reactive material (surfactant) and polymer will prepare in organic solvent.Suspension by pushing or being cast into certain shape, perhaps waters on level and smooth base then, and is for example on glass, thereby form thin slice, then thin slice carried out drying.The thin slice that obtains will separate with interim base and uses solvent or alpha-cyanoacrylate ester gum to be fixed on the reflector then, and the reflector that is covered by thin slice will heat under the temperature of 480 degree, and polymer can burnout in this process, only remaining fluorescent material cover layer.
In specific embodiment, and fluorescent material in the suspension (Y, Gd, Ce)
3Al
5O
12Be matrix with yttrium-gadolinium-cerium, the suspension in the carrene in the polycarbonate solution can obtain the different thin slice of thickness with the method for extruding, as shown in Figure 9.Conversion layer need have enough thickness to reach required value with the chromaticity coordinates that guarantees resulting mixed white light.Optical scattering process when using fluorescent material has determined the thickness of conversion layer, and thickness does not generally wait at the 5-500 micron, generally speaking between the 100-250 micron.
The sheet conversion layer that forms is fixed on moistening vinylacetate on the transducer of tubular, exerts pressure for the conversion layer of sheet with the formpiston of definite shape.Vinylacetate can allow conversion layer softening, so that bubble extrudes from the conversion layer below, thereby guarantees that conversion layer can be bonded on the reflector fully.The structure of reflector is uncomplicated, can cover with the mixture of transparent organic silicon polymer and fluorescent material, makes its burning then, and organosilicon polymer can not separate in the process of burning.But what must keep firmly in mind is, can convert blue light to the fluorescent material of orange-ruddiness, and when it was heated to 480 ° of C in air, it look can take place declines, up to inapplicable fully.We will use other the low polymer of ignition temperature in this case.Ignition temperature is at 260-540 ° of C in certain embodiments.
The outer surface of luminescence generated by light conversion layer can cover the protective layer of layer of transparent extraly, and to prevent entering moisture or oxygen in the conversion layer, because the fluorescent material of some types, for example sulphide fluorescent material is easy to be destroyed because of humidity.Protective layer can be made with any material transparent of energy block water or oxygen; for example; inorganic material-silicon dioxide, silica or aluminium oxide, even can also make with the composite material of organic compound material or organic compound and inorganic compound.We are more prone to make protective layer with silicon dioxide or silica.
Protective layer can be used as the optical lens between fluorescent powder grain edge and the air; with the radiation again in certain zone of the prompt radiation that reduces LED and fluorescent powder grain; reduce the light loss that is radiated fluorescent material self radiation on the fluorescent powder grain, thereby improve the luminous efficiency of light fixture.
Can use the method for processing fluorescent powder grain that protective layer is layed onto luminescence generated by light conversion layer outer surface, for example, form a layer thickness on fluorescent powder grain surface and be the zinc silicate film of 50-100nm to prevent the reflection at fluorescent powder grain edge.
Under the necessary condition condition, the aperture can not be subjected to the influence of moisture or oxygen to protect conversion layer with transparent window sealing, and its gas inside be filled or be extruded in the inside of light fixture can with inert gas.
The surface 10 of transducer 7 and the surface 6 of reflector 5 can be axisymmetric spherical, or axisymmetric ellipse, parabola or cylinder, its outer surface by heat dissipation base 2 blocks, and LED1 is positioned near the position on the cross spider on the heat dissipation base 2 of indication and the surface 10 of transducer 7, and distributes along cross spider.
The optimization of the optimization of surface 10 shapes of transducer and the position of LED and radiation direction helps to improve uniformity of light and the distribution of the angle of the radiation of sending from light fixture, LED projects radiation on the surface 10 of transducer from different angles, and the radiation of transducer 7 internal reflections is flowed out from aperture port.
Led chip, the family expenses chip EZBright that produces of the high-power blue-light LED chip SL-V-B45AC2 that produces of rising sun Mingguang City electricity or CREE Co., Ltd for example, its radiation direction schematic diagram has the feature (light and led chip normal to a surface cone angle are 90 °) of lambertian distribution or cone angle to be limited in α<90 °, for example, when the radiation output that is formed at the led chip surface is the quantum dot array structure.
The position of LED arranges more acceptantly like this on the heat dissipation base, that is, the symmetry axis of the radiation direction schematic diagram of LED and reflector symmetry axis are β 〉=90 °-α/2 degree angles and intersect.
But sub-fraction LED prompt radiation is arranged directly in the external communication of the aperture port of light fixture, in order to prevent that the LED radiation from directly projecting on the used gas, a projection 12 can be arranged on the heat dissipation base 2, and prompt radiation is outwards directly exported in its maskable light fixture, walks around the surface 10 of transducer 7.For prompt radiation is utilized more fully, the projection 12 on the above-mentioned heat dissipation base can comprise an additional reflector-level and smooth reflecting part 13 as mirror, and it can reflex to the prompt radiation that projects on it on surface 10 of reflector 7.
Figure 10 is the more detailed light fixture embodiment schematic diagram that comprises additional reflector.
The light fixture of this embodiment is that all elements that it has light fixture on Fig. 8 also comprise projection 12 and reflector 13 to the replenishing of Fig. 8.
Figure 11 comprises the light fixture embodiment schematic diagram of reflector than having described another one in greater detail, the profile of having showed the lamp base 2 after the amplification on the figure, LED is fixedly arranged on the base 2, preserved all elements corresponding on 8 (not keeping ratio) on the figure.
Additional speculum is the surface 15 of an inclination, and it is between the chip and transducer 7 of LED1, and the radiation that reflector can project the chip of LED1 on it reflexes on the transducer 7 fully, makes the radiation of light fixture output more even.
In order to increase conversion layer to the LED reflection of light, in the radiator surface of reflective optical system can be polishing or frosted so that radiation is more even, can also cover one deck on the reflective optical system has the very cover layer of high light reflectivity coefficient.Reflective optical system also can be independent eyeglass, and it wants the discrete heat device a little further, contacts but will produce heat by heat-conducting layer and radiator.The cover layer that has the high light reflectivity coefficient is made by following material: silver, aluminium, dichroic coating, titanium oxide and aluminium oxide, and wherein aluminium will link together to increase the reflection coefficient of aluminium with dichroic coating, and titanium oxide and aluminium oxide used gel method to obtain.
The chip of LED1 is positioned on the base 2 in the embodiment of this light fixture, normal towards chip surface is parallel (perhaps not parallel with the symmetry axis of reflector 6, but the angle of Xiang Jiaoing is little between the two), reflector 6 is that thickness is reflective film aluminium or silver of 0.15-0.2 micron, film is that the method with vacuum heat deposition is fixed on the inner surface of hemisphere cloche 17, reflector is to adhere on the hemisphere cover 19 of aluminum with heat-resisting and mixture 18 heat conduction springy, hemisphere cover 19 is second public electrode of LED1 chip, parallel with it lead 14 and polyimides short-term connect together chip and hemisphere cover, and spraying plating has metal 15 on the short-term.In order to improve light reflective properties, to be covered by the thin aluminium lamination of one deck on the sprayed metal 15 on the polyimides short-term, as additional reflector.The position that LED is set like this can make prompt radiation directly not project in people's the eye.
When making hemisphere cover 19 with kovar teleoseal or other alloy that similarly has good relatively thermal conductivity to reach low relatively thermal diffusion coefficient (the most approaching with the thermal diffusion coefficient of the fluorescent material that is used for transducer 7), can simplify the structure of light fixture, need not use hemisphere cover 17, to reduce cost.This method (perhaps other method) that need use the vacuum thermal spray is toward the inner surface plating of hemisphere cover 19 reflective film layer of aluminum or silver, directly spraying plating or pass thin film dielectric layer makes it precipitate into phosphor powder layer with the method for originally describing then.
When the material that school original text thermal diffusion coefficient is similarly arranged with aluminium, stainless steel, copper, brass or other (thermal diffusion coefficient of the transducer made from the plastics of being filled by fluorescent material 7 is close) is made cover 19, also can cover 17 making that just can finish whole light fixture.In order to reach this purpose, the inner surface of cover 19 plates layer of aluminum or silver-colored reflective film with the method for vacuum evaporating, and directly spraying plating or pass thin film dielectric layer adheres to it on plastics transducer of making in advance 7 then.
The chip of LED1 and power lug 14 can use now known, the technology that is applied to make the LED assembly with mixture 23 sealings.
Radiator 22 can be made with any suitable material, for example copper or aluminium.In order to increase radiating surface, radiator can be flange-cooled, for example, and as shown in figure 12.
Can make the semi-cylindrical shaped light fixture of linearity of white with the model of having used Semileds company shown in Figure 9 as the thin slice of the led chip of SL-V-B35AK, luminous efficiency depends on the thickness of thin slice, is the 160-200 lumens/watt.
List of references
1.Yamada,K.,Imai,Y.and?Ishii?K."Optical?Simulation?of?Light?Source?Devices?Composed?of?Blue?LEDs?and?YAG?Phosphor,"J.Light&Vis.Env.27(2),70-74(2003)。
2.Narendran,N.,Gu.Y.,Freyssinier,J.,Zhu,Y."Extracting?Phosphor-scattered?Photons?to?Improve?White?LED?Efficiency,"Phys.Stat.Sol.(a)202(6),R60-R62(2005)。
3.Zhu?Y.,N.Narendran,and?Y.Gu。"Investigation?of?the?optical?properties?of?YAG:Ce?phosphor"。Sixth?International?Conference?on?Solid?State?Lighting.Proceedings?of?SPIE.6337,63370S(2006)。
Claims (11)
1. a light fixture, comprise the prompt radiation light source, heat dissipation base, radiation converter, reflective optical system, wherein, the prompt radiation light source is made up of a more individual LED, LED is fixed on the heat dissipation base, radiation converter is the conversion layer of being made by certain material, transducer can convert the prompt radiation that LED projects on it to radiation again, reflective optical system can reflect the radiation that projects above it, radiation converter is close to the surface of reflector between prompt radiation light source and reflector, and reflective optical system and radiation converter are all away from the prompt radiation light source, this light fixture is characterised in that, porosely on the heat dissipation base be beneficial to radiation output, the surface of radiation converter is by the LED radiation, and the surface of reflective optical system is spill, its hole and LED on heat dissipation base, LED is positioned at the edge in hole.
2. light fixture as claimed in claim 1 is characterized in that, transducer face and reflector surface are as the figure of shape axisymmetricly, revolution ellipsoid for example, especially sphere or parabola are blocked by the plane parallel with hole on the heat dissipation base, and the plane in hole is vertical on main shaft and the heat dissipation base.
3. light fixture as claimed in claim 1 is characterized in that, transducer face and reflector surface are as being the figure of plane symmetry shape, cylindrical cross-section for example, blocked by the plane parallel with hole on the heat dissipation base, have symmetrical plane, vertical with the plane in hole on the heat dissipation base.
4. light fixture as claimed in claim 1 is characterized in that, on its heat dissipation base projection is arranged, and can shield prompt radiation, make its not directly the orifice flow from the heat dissipation base go out.
5. light fixture as claimed in claim 1 is characterized in that, the surface of the reflector of indication is the inner surface that the outside has the radiator of corner angle.
6. light fixture as claimed in claim 2 is characterized in that, the transducer of indication and the surface of reflector all are made up of a plurality of level and smooth facets or arcuation material.
7. radiator as claimed in claim 3 is characterized in that, the heat dissipation base of prompt radiation light source is the integral body of a band reflector.
8. light fixture as claimed in claim 1 is characterized in that, the transducer face of projection is relative with its concave surface that is shone by prompt radiation, and the reflector surface of protruding transducer face and depression is separated by transparent optical medium.
9. light fixture as claimed in claim 4 is characterized in that, the projection on the heat dissipation base comprise level and smooth can catoptrical part as mirror, it can project the prompt radiation that projects on it on transducer face opposed with it.
10. light fixture as claimed in claim 3 is characterized in that, LED is fixed on the heat dissipation base, and the axle of each LED radiation projecting direction schematic diagram intersects with the symmetry axis of reflector, and its angle is 90 degree, perhaps less than 90 degree.
11. light fixture as claimed in claim 3, it is characterized in that, LED is fixed on the heat dissipation base, the axle of the radiation projecting direction schematic diagram of each LED is parallel with the symmetry axis of reflector, perhaps the angle of Xiang Jiaoing is little, heat dissipation base between transducer face and LED contains the part as the catoptrical inclination of mirror energy, and it can project the prompt radiation that projects on it on transducer face opposed with it.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2011100487 | 2011-01-13 | ||
RU2011100487/28A RU2452059C1 (en) | 2011-01-13 | 2011-01-13 | Light-emitting diode source of white light with remote photoluminescent reflecting converter |
PCT/RU2011/001006 WO2013039418A1 (en) | 2011-01-13 | 2011-12-20 | White-light light-emitting diode lamp with a remote reflective photoluminescent converter |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103348476A true CN103348476A (en) | 2013-10-09 |
CN103348476B CN103348476B (en) | 2016-12-28 |
Family
ID=46231808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180064616.XA Expired - Fee Related CN103348476B (en) | 2011-01-13 | 2011-12-20 | White LED light source with luminescence generated by light transducer |
Country Status (8)
Country | Link |
---|---|
US (1) | US9136444B2 (en) |
EP (1) | EP2665099A4 (en) |
JP (1) | JP6045079B2 (en) |
KR (1) | KR20140053837A (en) |
CN (1) | CN103348476B (en) |
CA (1) | CA2824309A1 (en) |
RU (1) | RU2452059C1 (en) |
WO (1) | WO2013039418A1 (en) |
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Also Published As
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KR20140053837A (en) | 2014-05-08 |
CA2824309A1 (en) | 2013-03-21 |
US20130306998A1 (en) | 2013-11-21 |
EP2665099A4 (en) | 2017-11-22 |
WO2013039418A1 (en) | 2013-03-21 |
EP2665099A1 (en) | 2013-11-20 |
JP6045079B2 (en) | 2016-12-14 |
US9136444B2 (en) | 2015-09-15 |
CN103348476B (en) | 2016-12-28 |
RU2452059C1 (en) | 2012-05-27 |
JP2014505982A (en) | 2014-03-06 |
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